Engineering Electronic Structure of Single-Atom Pd Site on Ti_(0.87)O_(2)Nanosheet via Charge Transfer Enables C-Br Cleavage for Room-Temperature Suzuki Coupling  

作　　者：Yangxin Jin Fei Lu Ding Yi Junmeng Li Fengchu Zhang Tian Sheng Fei Zhan Ya’nan Duan Gaochao Huang Jinyang Dong Bo Zhou Xi Wang Jiannian Yao 

机构地区：[1]Department of Physics,School of Science,Beijing Jiaotong University,Beijing 100044 [2]School of Chemical Engineering and Technology,Molecular Plus and Collaborative Innovation Center of Chemical Science and Engineering,Tianjin University,Tianjin 300072 [3]College of Chemistry and Materials Science,Anhui Normal University,Wuhu 241000 [4]Chemistry and Chemical Engineering Guangdong Laboratory,Shantou 515031 [5]Key Laboratory of Photochemistry,Beijing National Laboratory for Molecular Sciences(BNLMS),Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190

出　　处：《CCS Chemistry》2021年第6期1453-1462,共10页中国化学会会刊（英文）

基　　金：This study was supported financially by the National Natural Science Foundation of China(grant nos.91961125,21905019,and 21903001);the Fundamental Research Funds for the Central Universities(grant nos.2018JBZ107 and 2019RC035);the Ministry of Science and Technology of China(grant no.2018YFE0124600);the Chemistry and Chemical Engineering Guangdong Laboratory(grant no.1932004);the Natural Science Foundation of Anhui Province(grant no.1908085QB58)。

摘　　要：The palladium(Pd)-catalyzed Suzuki reaction is widely applied in the pharmaceutical industry,where constructing highly active and low-cost Pd sites are impendent.Here,we report the fabrication of a heterogeneous Pd/Tio2 catalyst via engineering of an electronic structure of a single Pd_(1)atom on monolayered Ti_(0.87)O_(2)nanosheet(Pd_(1)-Ti_(0.87)O_(2)).This catalyst motivated the kinetically sluggish C-Br cleavage,thus boosting the Suzuki reaction at room temperature.Pd_(1)-Ti_(0.87)O_(2)exhibited an outstanding activity with turnover frequency(TOF)of 11,110 h-1,exceeding that of PdCl_(2)and Pd(OAc)_(2)catalysts by a factor of>200.Various in situ techniques were employed to investigate the C-Br activation process,which showed that Pd_(1)kinetic-feasibly dissociated the chemisorbed bromobenzene,especially the C-Br bond cleavage.Theoretical calculations further revealed that the improved activity is ascribed to the optimized charge state of Pd_(1)within the Pd_(1)O4 realm via charge transfer.

关 键 词：charge transfer Pd single atom monolayered Ti_(0.87)O_(2)nanosheet Suzuki coupling C-Br cleavage 

分 类 号：O64[理学—物理化学]